1-Benzothiazolyl-5-amino-imidazolidinones

ABSTRACT

This invention discloses new compounds of the formula ##STR1## wherein X is selected from the group consisting of alkyl, halogen, haloalkyl and alkoxy; n is an integer from 0 to 2; R 1  is selected from the group consisting of alkyl, alkenyl, haloalkyl and ##STR2## wherein R 4  and R 5  are each selected from the group consisting of hydrogen and alkyl; and R 2  and R 3  are each selected from the group consisting of hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl and ##STR3## WHEREIN P IS THE INTEGER 0 OR 1; Y is selected from the group consisting of alkyl, alkoxy, alkylthio, halogen, haloalkyl, nitro and cyano; and m is an integer from 0 to 3.

This invention relates to new compositions of matter and morespecifically relates to new chemical compounds of the formula ##STR4##wherein X is selected from the group consisting of alkyl, halogen,haloalkyl and alkoxy; n is an integer from 0 to 2; R¹ is selected fromthe group consisting of alkyl, alkenyl, haloalkyl and ##STR5## whereinR⁴ and R⁵ are each selected from the group consisting of hydrogen andalkyl; and R² and R³ are each selected from the group consisting ofhydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl,cycloalkyl and ##STR6## WHEREIN P IS THE INTEGER 0 OR 1; Y is selectedfrom the group consisting of alkyl, alkoxy, alkylthio, halogen,haloalkyl, nitro and cyano; and m is an integer from 0 to 3.

The compounds of the present invention are useful as herbicides.

In a preferred embodiment of the present invention X is selected fromthe group consisting of lower alkyl, chlorine, bromine, fluorine, lowerchloroalkyl, lower bromoalkyl, trifluoromethyl and lower alkoxy; n is aninteger from 0 to 2; R¹ is selected from the group consisting of loweralkyl, lower alkenyl, lower haloalkyl and ##STR7## wherein R⁴ and R⁵ areeach selected from the group consisting of hydrogen and alkyl of up to 3carbon atoms; and R² and R³ are each selected from the group consistingof hydrogen, lower alkyl, lower alkenyl, lower haloalkyl, lowerhydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atomsand ##STR8## wherein p is the integer 0 or 1; Y is selected from thegroup consisting of lower alkyl, lower alkoxy, lower alkylthio, halogen,lower chloroalkyl, lower bromoalkyl, trifluoromethyl, nitro and cyano;and m is an integer from 0 to 3.

The term "lower" as used herein designates a straight or branched carbonchain of up to 6 carbon atoms.

The compounds of the present invention can be prepared by reacting acompound of the formula ##STR9## wherein X, n and R¹ are as heretoforedescribed, with an amine of the formula ##STR10## wherein R² and R³ areas heretofore described. This reaction can be effected by combining thecompound of formula II with an about equimolar amount or excess molaramount of the amine of formula III in an inert organic reaction medium,such as heptane or toluene, and then heating the reaction mixture, withstirring, at its reflux temperature and azeotropically removing thewater of reaction. After this time the reaction mixture can be cooled,and the desired product can be recovered by filtration if formed as aprecipitate or upon evaporation of the organic reaction medium ifsoluble therein. The product can then be purified by conventional meanssuch as recrystallization and the like.

The compound of formula II can be readily prepared by heating a compoundof the formula ##STR11## wherein X, n and R¹ are as heretoforedescribed, in a dilute, aqueous, acidic reaction medium for a period offrom about 10 to about 60 minutes. Temperatures of from about 60° C tothe reflux temperature of the reaction mixture can be utilized. Thereaction medium can comprise a dilute, aqueous inorganic acid such ashydrochloric acid at a concentration of from about 0.5 to about 10percent. Lower water-miscible alkanols can also be suitably added to thereaction medium to aid in the dissolution of the starting materials.After completion of the reaction the desired product can be recoveredupon evaporation of the solvents used if soluble therein or byfiltration if formed as a precipitate. This product can then be used assuch or can be further purified by standard techniques such astrituration, recrystallization, washing and the like.

The compounds of formula IV can be prepared by reacting a molar amountof an isocyanate dimer of the formula ##STR12## wherein X and n are asheretofore described, with about two molar amounts of a dimethyl acetalof the formula ##STR13## wherein R¹ is as heretofore described. Thisreaction can be effected by combining the isocyanate dimer of formula V,dissolved in an inert organic solvent such as benzene, with the acetalof formula VI at room temperature and stirring the resulting mixture fora period of about 1/2 to about 4 hours. After this time the reactionmixture can be filtered and the filtrate stripped of solvent to yieldthe desired product. This product can be used as such or furtherpurified if desired by standard techniques.

The isocyanate dimer of formula V can be prepared by reacting abenzothiazole of the formula ##STR14## wherein X and n are as heretoforedescribed, with phosgene. This reaction can be effected by adding aslurry or solution of the benzothiazole in a suitable organic solventsuch as ethyl acetate to a solution of phosgene in a similar solvent.The resulting mixture can then be heated at reflux for a period of from1/2 to 2 hours. The desired product can then be recovered by filtrationif formed as a precipitate or upon evaporation of the organic solvent ifsoluble therein.

Exemplary suitable compounds of formula VI for preparing the compoundsof the present invention are the dimethyl acetal of2-methylaminoacetaldehyde, the dimethyl acetal of2-ethylaminoacetaldehyde, the dimethyl acetal of2-propylaminoacetaldehyde, the dimethyl acetal of2-allylaminoacetaldehyde, the dimethyl acetal of2-chloromethylaminoacetaldehyde, the dimethyl acetal of2-β-bromoethylaminoacetaldehyde, the dimethyl acetal of2-propargylaminoacetaldehyde and the like.

Exemplary suitable compounds of formula VII for preparing the compoundsof this invention are 2-aminobenzothiazole,2-amino-5-methylbenzothiazole, 2-amino-6-chlorobenzothiazole,2-amino-4,5-dimethylbenzothiazole, 2-amino-7-bromobenzothiazole,2-amino-6-methoxybenzothiazole, 2-amino-66-fluorobenzothiazole,2-amino-4-methyl-6-chloromethylbenzothiazole,2-amino-4-chloromethylbenzothiazole,2-amino-5-β-bromoethylbenzothiazole,2-amino-6-trifluoromethylbenzothiazole and the like.

The manner in which the compounds of the present invention can beprepared is more specifically illustrated in the following examples.

EXAMPLE 1 Preparation of Benzothiazol-2-yl Isocyanate Dimer

A saturated solution of phosgene in ethyl acetate (1200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. 2-Aminobenzothiazole (100.0 grams;0.67 mole) is then added with stirring. After the addition is completed,the reaction mixture is heated at reflux for a period of about one hour.After this time the reaction mixture is evaporated to dryness to yieldthe desired product benzothiazol-2-yl isocyanate dimer as a yellow solidhaving a melting point of 250° to 252° C.

EXAMPLE 2 Preparation of the Dimethyl Acetal of2-(1-Methyl-3-benzothiazol-2-ylureido)acetaldehyde

Benzothiazol-2-yl isocyanate dimer prepared in Example, 1 benzene (300ml) and the dimethyl acetal of 2-methylaminoacetaldehyde (80 grams; 0.67mole) are charged into a glass reaction vessel equipped with amechanical stirrer and thermometer. The reaction mixture is stirred atroom temperature for a period of about one hour. After this time themixture is filtered to remove a yellow solid that has formed. Thefiltrate is then stripped of solvent under reduced pressure to yield thedesired product the dimethyl acetal of2-(1-methyl-3-benzothiazol-2-ylureido)-acetaldehyde as an oil.

EXAMPLE 3 Preparation of the1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-(1-methyl-3-benzothiazol-2-ylureido)acetaldehyde (150 grams), methanol(750 ml), water (750 ml) and concentrated hydrochloric acid (75 ml) arecharged into a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. The reaction mixture is blanketed withnitrogen gas is heated at reflux for a period of about 15 minutes. Afterthis time the mixture is stripped of most of the solvents, and theresidue is combined with aqueous sodium bicarbonate (500 ml). Themixture is then extracted with ethyl acetate, and the resulting solutionis dried over anhydrous magnesium sulfate. The dried solution is thenstripped of solvent to yield the desired product1-benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one as ayellow solid melting at 168° to 170° C.

EXAMPLE 4 Preparation of1-Benzothiazol-2-yl-3-methyl-5-ethylamino-1,3-imidazolin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. Ethylamine (0.1 mole) is added to the reaction vessel, andthe mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-ethylamino-1,3-imidazolidin-2-one as theresidue.

EXAMPLE 5 Preparation of 5-Methylbenzothiazol-2-yl Isocyanate Dimer

A saturated solution of phosgene in ethyl acetate (200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. 2-Amino-5-methylbenzothiazole (0.1mole) is added with stirring. After the addition is completed, thereaction mixture is heated at reflux for a period of about one hour.After this time the mixture is cooled, and the solid product formed isrecovered by filtration. The solid is then dried to yield the desiredproduct 5-methylbenzothiazol-2-yl isocyanate dimer.

EXAMPLE 6 Preparation of the Dimethyl Acetal of2-[1-Methyl-3-(5-methylbenzothiazol-2-yl)ureido]acetaldehyde

5-Methylbenzothiazol-2-yl isocyanate dimer (0.1 mole), the dimethylacetal of 2-methylaminoacetaldehyde (0.2 mole) and benzene (100 ml) arecharged into a glass reaction vessel equipped with a mechanical stirrerand thermometer. The reaction mixture is stirred at ambient temperaturesfor a period of about one hour. After this time the reaction mixture isfiltered, and the filtrate is stripped of solvent to yield the desiredproduct the dimethyl acetal of2-[1-methyl-3-(5-methylbenzothiazol-2-yl)ureido]acetaldehyde as theresidue.

EXAMPLE 7 Preparation of1-(5-Methylbenzothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-[1-methyl-3-(5-methylbenzothiazol-2-yl)ureido]acetaldehyde (15 grams),water (200 ml), methanol (200 ml) and concentrated hydrochoric acid (10ml) are charged into a glass reaction vessel equipped with a mechanicalstirrer, thermometer and reflux condenser. The reaction mixture isheated at reflux for a period of about 15 minutes. after this time thereaction mixture is stripped of solvents under reduced pressure, leavinga residue. This residue is recrystallized to yield the desired product1-(5-methylbenzothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one.

EXAMPLE 8 Preparation of1-(5-Methylbenzothiazol-2-yl)-3-methyl-5-t-butylamino-1,3-imidazolidin-2-one

1-(5-Methylbenzothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one(0.1 mole) and heptane (100 ml) are charged into a glass reaction vesselequipped with a mechanical stirrer, thermometer, Dean-Stark trap andreflux condenser. t-Butylamine (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-(5-methylbenzothiazol-2-yl)-3-methyl-5-t-butylamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 9 Preparation of 6-Chlorobenzothiazol-2-yl Isocyanate Dimer

A saturated solution of phosgene in ethyl acetate (200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. 2-Amino-6-chlorobenzothiazole (0.1mole) is added with stirring. After the addition is completed, thereaction mixture is heated at reflux for a period of about one hour.After this time the mixture is cooled, and the solid product formed isrecovered by filtration. The solid is then dried to yield the desiredproduct 6-chlorobenzothiazol-2-yl isocyanate dimer.

EXAMPLE 10 Preparation of the Dimethyl Acetal of2-[1-Allyl-3-(6-chlorobenzothiazol-2-yl)ureido]acetaldehyde

6-Chlorobenzothiazol-2-yl isocyanate dimer (0.1 mole), the dimethylacetal of 2-allylaminoacetaldehyde (0.2 mole) and benzene (100 ml) arecharged into a glass reaction vessel equipped with a mechanical stirrerand thermometer. The reaction mixture is stirred at ambient temperaturesfor a period of about one hour. After this time the reaction mixture isfiltered, and the filtrate is stripped of solvent to yield the desiredproduct the dimethyl acetal of2-[1-allyl-3-(6-chlorobenzothiazol-2-yl)ureido]acetaldehyde as theresidue.

EXAMPLE 11 Preparation of1-(6-Chlorobenzothiazol-2-yl)-3-allyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-[1-allyl-3-(6-chlorobenzothiazol-2-yl)ureido]acetaldehyde (15 grams),water (200 ml), methanol (200 ml) and concentrated hydrochloric acid (10ml) are charged into a glass reaction vessel equipped with a mechanicalstirrer, thermometer and reflux condenser. The reaction mixture isheated at reflux for a period of about 15 minutes. After this time thereaction mixture is stripped of solvents under reduced pressure, leavinga residue. This residue is recrystallized to yield the desired product1-(6-chlorobenzothiazol-2-yl)-3-allyl-5-hydroxy-1,3-imidazolidin-2-one.

EXAMPLE 12 Preparation of1-(6-Chlorobenzothiazol-2-yl)-3-allyl-5-allylamino-1,3-imidazolidin-2-one

1-(6-Chlorobenzothiazol-2-yl)-3-allyl-5-hydroxy-1,3-imidazolidin-2-one(0.1 mole) and heptane (100 ml) are charged into a glass reaction vesselequipped with a mechanical stirrer, thermometer, Dean-Stark trap andreflux condenser. Allylamine (0.1 mole) is added to the reaction vessel,and the mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-(6-chlorobenzothiazol-2-yl)-3-allyl-5-allylamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 13 Preparation of 7-Bromobenzothiazol-2-yl Isocyanate Dimer

A saturated solution of phosgene in ethyl acetate (200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer, thethermometer and reflux condenser. 2-Amino-7-bromobenzothiazole (0.1mole) is added with stirring. After this time the mixture is cooled, andthe solid product formed is recovered by filtration. The solid is thendried to yield the desired product 7-bromobenzothiazol-2-yl isocyanatedimer.

EXAMPLE 14 Preparation of the Dimethyl Acetal of2-[1-Propargyl-3-(7-bromobenzothiazol-2-yl)ureido]acetaldehyde

7-Bromobenzothiazol-2-yl isocyanate dimer (0.1 mole), the dimethylacetal of 2-propargylaminoacetaldehyde (0.2 mole) and benzene (100 ml)are charged into a glass reaction vessel equipped with a mechanicalstirrer and thermometer. The reaction mixture is stirred at ambienttemperatures for a period of about one hour. After this time thereaction mixture is filtered, and the filtrate is stripped of solvent toyield the desired product the dimethyl acetal of2-[1-propargyl-3-(7-bromobenzothiazol-2-yl)ureido]acetaldehyde as theresidue.

EXAMPLE 15 Preparation of1-(7-Bromobenzothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-[1-propargyl-3-(7-bromobenzothiazol-2-yl)ureido]acetaldehyde (15grams), water (200 ml), methanol (200 ml) and concentrated hydrochloricacid (10 ml) are charged into a glass reaction vessel equipped with amechanical stirrer, thermometer and reflux condenser. The reactionmixture is heated at reflux for a period of about 15 minutes. After thistime the reaction mixture is stripped of solvents under reducedpressure, leaving a residue. This residue is recrystallized to yield thedesired product1-(7-brmobenzothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin2-one.

EXAMPLE 16 Preparation of1-(7-Bromobenzothiazol-2-yl)-3-propargyl-5-β-chloroethylamino-1,3-imidazolidin-2-one

1-(7-Bromobenzothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin-2-one(0.1 mole) and heptane (100 ml) are charged into a glass reaction vesselequipped with a mechanical stirrer, thermometer, Dean-Stark trap andreflux condenser. β-Chloroethylamine (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-(7-bromobenzothiazol-2-yl)-3-propargyl-5-β-chloroethlamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 17 Preparation of 4-Methoxybenzothiazol-2-yl Isocyanate Dimer

A saturated solution of phosgene in ethyl acetate (200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. 2-Amino-4-methoxybenzothiazole (0.1mole) is added with stirring. After the addition is completed, thereaction mixture is heated at reflux for a period of about one hour.After this time the mixture is cooled, and the solid product formed isrecovered by filtration. The solid is then dried to yield the desiredproduct 4-methoxybenzothiazol-2-yl isocyanate dimer.

EXAMPLE 18 Preparation of the dimethyl Acetal of2-[1-Ethyl-3-(4-methoxybenzothiazol-2-yl)ureido]acetaldehyde

4-Methoxybenzothiazol-2-yl isocyanate dimer (0.1 mole), the dimethylacetal of 2-ethylaminoacetaldehyde (0.2 mole) and benzene (100 ml) arecharged into a glass reaction vessel equipped with a mechanical stirrerand thermometer. The reaction mixture is stirred at ambient temperaturesfor a period of about one hour. After this time the reaction mixture isfiltered, and the filtrate is stripped of solvent to yield the desiredproduct the dimethyl acetal of2-[1-ethyl-3-(4-methoxybenzothiazol-2-yl)ureido]acetaldehyde as theresidue.

EXAMPLE 19 Preparation of1-(4-Methoxybenzothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-[1-ethyl-3-(4-methoxybenzothiazol-2-yl)ureido]acetaldehyde (15 grams),water (200 ml), methanol (200 ml) and concentrated hydrochloric acid (10ml) are charged into a glass reaction vessel equipped with a mechanicalstirrer, thermometer and reflux condenser. The reaction mixture isheated at reflux for a period of about 15 minutes. After this time thereaction mixture is stripped of solvents under reduced pressure, leavinga residue. This residue is recrystallized to yield the desired product1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin2-one.

EXAMPLE 20 Preparation of1-(4-Methoxybenzothiazol-2-yl)-3-ethyl-5-β-hydroxyethylamino-1,3-imidazolidin-2-one

1-(4-Methoxybenzothiazol-2-yl)-3-ethyl-5-hydroxy1,3-imidazlidin-2-one(0.1 mole) and heptane (100 ml) are charged into a glass reaction vesselequipped with a mechanical sttirrer, thermometer, Dean-Stark trap andreflux condenser. β-Hydroxyethylamine (0.1 mole) is added to thereaction vessel, and the mixture is heated at reflux while removing thewater as it is formed. After no more water is given off, the reactionmixture is stripped of solvent reduced pressure to yield the desiredproduct1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-β-hydroxyethylamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 21 Preparation of 5-Fluorobenzothiazol-2-yl Isocyanate Dimer

A saturated solution of phosgene in ethyl acetate (200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. 2-Amino-5-fluorobenzothiazole (0.1mole) is added with stirring. After the addition is completed, thereaction mixture is heated at reflux for a period of about one hour.After this time the mixture is cooled, and the solid product formed isrecovered by filtration. The solid is then dried to yield the desiredproduct 5-fluorobenzothiazol -2-yl isocyanate dimer.

EXAMPLE 22 Preparation of the Dimethyl Acetal of2-[1-Chloromethyl3-(5-fluorobenzothioazol-2-yl)ureido]acetaldehyde

5-Fluorobenzothiazol-2-yl isocyanate dimer (0.1 mole), the dimethylacetal of 2-chloromethylaminoacetaldehyde (0.2 mole) and benzene (100ml) are charged into a glass reaction vessel equipped with a mechanicalstirrer and thermometer. The reaction mixture is stirred at ambienttemperatures for a period of about one hour. After this time thereaction mixture is filtered, and the filtrate is stripped of solvent toyield the desired product the dimethyl acetal of2-[1-chloromethyl-3-(5-fluorobenzothiazol-2-yl)ureido]acetaldehyde asthe residue.

EXAMPLE 23 Preparation of1-(5-Fluorobenzothiazol-2-yl)-3-chloromethyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-[1-chloromethyl-3-(5-fluorobenzothiazol-2-yl)ureido]acetaldehyde (15grams), water (200 ml), methanol (200 ml) and concentrated hydrochloricacid (10 ml) are charged into a glass reaction vessel equipped with amechanical stirrer, thermometer and reflux condenser. The reactionmixture is heated at heated at reflux for a period of about 15 minutes.After this time the reaction mixture is stripped of solvents underreduced pressure, leaving a residue. This residue is recrystallized toyield the desired product1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-hydroxy-1,3-imidazolidin-2-one.

EXAMPLE 24 Preparation of1-(5-Fluorobenzothiazol-2-yl)-3-chloromethyl-5-methoxymethylamino-1,3-imidazolidin-2-one

1-(5-Fluorobenzothiazol-2-yl-3-chloromethyl-5-hydroxy-1,3-imidazolidin-2-one(0.1 mole) and heptane (100 ml are charged into a glass reaction vesselequipped with a mechanical stirrer, thermometer, Dean-Stark trap andreflux condenser. Methoxymethylamine (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-methoxymethylamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 25 Preparation of 5-Trifluoromethyl-benzothiazol-2-yl IsocyanateDimer

A saturated solution of phosgene in ethyl acetate (200 ml) is chargedinto a glass reaction vessel equipped with a mechanical stirrer,thermometer and reflux condenser. 2-Amino-5-trifluoromethylbenzothiazole(0.1 mole) is added with stirring. After the addition is completed, thereaction mixture is heated at reflux for a period of about one hour.After this time the mixture is cooled, and the solid product formed isrecovered by filtration. The solid is then dried to yield the desiredproduct 5-trifluoromethylbenzothiazol2-yl isocyanate dimer.

EXAMPLE 26 Preparation of the Dimethyl Acetal of2-[1-β-Bromoethyl-3-(5-trifluoromethylbenzothiazol-2-yl)ureido]acetaldehyde

5-Trifluoromethylbenzothiazol-2-yl isocyanate dimer (0.1 mole), thedimethyl acetal of 2-β-bromoethylaminoacetaldehyde (0.2 mole) andbenzene (100 ml) are charged into a glass reaction vessel equipped witha mechanical stirrer and thermometer. The reaction mixture is stirred atambient temperatures for a period of about one hour. After this time thereaction mixture is filtered, and the filtrate is stripped of solvent isyield the desired product the dimethyl acetal of2-[1-β-bromoethyl-3-(5-trifluoromethylbenzothiazol-2-yl)ureido]acetaldehydeas the residue.

EXAMPLE 27 Preparation of1-(5-Trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one

The dimethyl acetal of2-[1-β-bromoethyl-3-(5-trifluoromethylbenzothiazol-2-yl)ureido]acetaldehyde(15 grams), water (200 ml), methanol (200 ml) and concentratedhydrochloric acid (10 ml) are charged into a glass reaction vesselequipped with a mechanical stirrer, thermometer and reflux condenser.The reaction mixture is heated at reflux for a period of about 15minutes. After this time the reaction mixture is stripped of solventsunder reduced pressure, leaving a residue. This residue isrecrystallized to yield the desired product1-(5-trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl5-hydroxy-1,3-imidazolidin-2-one.

EXAMPLE 28 Preparation of1-(5-Trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-cyclopropylamino-1,3-imidazolidin-2-one

1-(5-Trifluoromethylbenzothiazol-2-yl)-3-β-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one(0.1 mole) and heptane (100 ml) are charged into a glass reaction vesselequipped with a mechanical stirrer, thermometer, Dean-Start trap andreflux condenser. Cyclopropylamine (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-(5-trifluoromethylbenzothiazol2-yl)-3-β-bromoethyl-5-cyclopropylamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 29 Preparation of1-Benzothiazol-2-yl-3-methyl-5-anilino-1,3-imidazolin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imiazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. Aniline (0.1 mole) is added to the reaction vessel, and themixture is heated at reflux while removing the water as it is formed.After no more water is given off, the reaction mixture is stripped ofsolvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-anilino-1,3-imidazolidin-2-one as theresidue.

EXAMPLE 30 Preparation of1-Benzothiazol-2-yl-3-methyl-5-dimethylamino-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazoidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. Dimethylamine (0.1 mole) is added to the reaction vessel, andthe mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-dimethylamino-1,3-imidazolidin-2-one asthe residue.

EXAMPLE 31 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(2-methylanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 2-Methylaniline (0.1 mole) is added to the reaction vessel,and the mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(2-methylanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 32 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(2,6-dimethoxyanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechaical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 2,6-Dimethoxyaniline (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(2,6-dimethoxyanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 33 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(4-methylthioanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 4-Methylthioaniline (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(4-methylthioanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 34 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(3,4-dichloroanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 3,4-Dichloroaniline (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(3,4-dichloroanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 35 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(4-trifluoromethylanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 4-Trifluoromethylaniline (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(4-trifluoromethylanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 36 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(3-nitroanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 3-Nitroaniline (0.1 mole) is added to the reaction vessel,and the mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(3-nitroanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 37 Preparation of1-Benzothiazol-2-yl-3-methyl-5-(4-cyanoanilino)-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hdroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. 4-Cyanoaniline (0.1 mole) is added to the reaction vessel,and the mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-(4 -cyanoanilino)-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 38 Preparation of1-Benzothiazol-2-yl-3-methyl-5-benzylamino-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. Benzylamine (0.1 mole) is added to the reaction vessel, andthe mixture is heated at reflux while removing the water as it isformed. After no more water is given off, the reaction mixture isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-benzylamino-1,3-imidazolidin-2-one as theresidue.

EXAMPLE 39 Preparation of1-Benzothiazol-2-yl-3-methyl-5-N-methyl-N-ethoxymethylamino-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. N-MethylN-ethoxymethylamine (0.1 mole) is added to thereaction vessel, and the mixture is heated at reflux while removing thewater as it is formed. After no more water is given off, the reactionmixture is stripped of solvent under reduced pressure to yield thedesired product1-benzothiazol-2-yl-3-methyl-5-N-methyl-N-ethoxymethylamino-1,3-imidazolidin-2-oneas the residue.

EXAMPLE 40 Preparation of1-Benzothiazol-2-yl-3-methyl-5-N-methyl-N-benzylamino-1,3-imidazolidin-2-one

1-Benzothiazol-2-yl-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole)and heptane (100 ml) are charged into a glass reaction vessel equippedwith a mechanical stirrer, thermometer, Dean-Stark trap and refluxcondenser. N-MethylN-benzylamine (0.1 mole) is added to the reactionvessel, and the mixture is heated at reflux while removing the water asit is formed. After no more water is given off, the reaction mixture, isstripped of solvent under reduced pressure to yield the desired product1-benzothiazol-2-yl-3-methyl-5-N-methyl-N-benzylamino-1,3-imidazolidin-2-oneas the residue.

Additional compounds within the scope of the present invention which canbe prepared according to the procedures detailed in the foregoingexamples include1-(5-ethylbenzothiazol-2-yl)-3-ethyl-5-dimethylamino-1,3-imidazolidin-2-one,1-(6-propylbenzothiazol-2-yl)-3-propyl-5-diethylamino-1,3-imidazolidin-2-one,1-(7-butylbenzothiazol-2-yl)-3-butyl-5-dipropylamino-1,3-imidazolidin-2-one,1-(5-hexylbenzothiazol-2-yl)-3-pentyl-5-dibutylamino-1,3-imidazolidin-2-one,1-(6-ethoxybenzothiazol-2-yl)-3-hexyl-5-dihexylamino-1,3-imidazolidin-2-one,1-(6-propoxybenzothiazol-2-yl)-3-but-3-enyl-5-N-methyl-N-ethylamino-1,3-imidazolidin-2-one,1-(5-butoxybenzothiazol-2-yl)-3-pent-4-enyl-5-allylamino-1,3-imidazolidin-2-one,1-(7-hexyloxybenzothiazol-2-yl)-3-hex-4-enyl-5-but-3-enylamino-1,3-imidazolidin-2-one,1-(7-chloromethylbenzothiazol-2-yl)-3-chloromethyl-5-pent-4-enylamino-1,3-imidazolidin-2-one,1-(5-β-bromoethylbenzothiazol-2-yl)-3-β-chloroethyl-5-hex-4-enylamino-1,3-imidazolin-2-one,1-(6-dichlorobenzothiazol-2-yl)-3-β-bromoethyl-5-γ-bromopropylamino-1,3-imidazolidin-2-one,1-(5-methyl-6-chlorobenzothiazol-2-yl)-3-γ-chloropropyl-5-δ-bromobutylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-ω-chlorohexyl-5-propoxymethylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-but-3-ynyl-5-butoxymethylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-pent-4-ynyl-5-hexyloxymethylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-hex-5-ynyl-5-β-ethoxyethylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-γ-ethoxypropylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-δ-methoxybutylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl5-β-hydroxyethylamino-1,3-imidazolidin-2-one,1-benzothiazol2-yl-3-methyl-5-γ-hydroxypropylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-δ-hydroxybutylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-β-hydroxyhexyl-amino-1,3-imidazolidin-2-one,1benzothiazol-2-yl-3-methyl-5-cyclobutylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-cyclohexylamino-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-cyclopentylamino-1,3,-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-cycloheptylamino-1,3-imidazolidin2-one,1-benzothiazol-2-yl-3-methyl-5-(2-ethylanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(3-propylanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl5-(4-butylanilino)-1,3-imidazolidin-2-one,1-benzothiazol2-yl-3-methyl-5-(4-hexylanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(2,6-diethoxyanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(4-propoxyanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(3-hexyloxyanilino)-1,3-imidazolidin-2-one,1-benzothiazol2-yl-3-methyl-5-(4-ethylthioanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(3-propylthioanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(4-butylthioanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl5-(4-hexylthioanilino)-1,3-imidazolidin-2-one,1-benzothiazol2-yl-3-methyl-5-(3,4-dichloroanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(3,4-dibromoanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(4-fluoroanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(4-iodoanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(2-β-bromoethylanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(4-γ-chloropropylanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(4-β,β,β-trifluoroethylanilino)-1,3-imidazolidin-2-one,1-benzothiazol-2-yl-3-methyl-5-(2,4,6-trimethylanilino)-1,3-imidazolidin-2-oneand the like.

For practical use as herbicides the compounds of this invention aregenerally incorporated into herbicidal compositions which comprise aninert carrier and a herbicidally toxic amount of such a compound. Suchherbicidal compositions, which can also be called formulations, enablethe active compound to be applied conveniently to the site of the weedinfestation in any desired quantity. These compositions can be solidssuch as dusts, granules, or wettable powders; or they can be liquidssuch as solutions, aerosols, or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the talcs, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water or oil to anydesired concentration of the active compound, can be prepared byincorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofherbicides can be dispersed under super-atmospheric pressure asaerosols. However, preferred liquid herbicidal compositions areemulsifiable concentrates, which comprise an active compound accordingto this invention and as the inert carrier, a solvent and an emulsifier.Such emulsifiable concentrates can be extended with water and/or oil toany desired concentration of active compound for application as spraysto the site of the weed infestation. The emulsifiers most commonly usedin these concentrates are nonionic or mixtures of nonionic with anionicsurface-active agents. With the use of some emulsifier systems aninverted emulsion (water in oil) can be prepared for direct applicationto weed infestations.

A typical herbicidal composition according to this invention isillustrated by the following example, in which the quantities are inparts by weight.

    ______________________________________                                        Example 41                                                                    Preparation of a Dust                                                         ______________________________________                                        Product of Example 4  10                                                      Powdered Talc         90                                                      ______________________________________                                    

The above ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the weed infestation.

The compounds of this invention can be applied as herbicides in anymanner recognized by the art. One method for the control of weedscomprises contacting the locus of said weeds with a herbicidalcomposition comprising an inert carrier and as an essential activeingredient, in a quantity which is herbicidally toxic to said weeds, acompound of the present invention. The concentration of the newcompounds of this invention in the herbicidal compositions will varygreatly with the type of formulation and the purpose for which it isdesigned, but generally the herbicidal compositions will comprise fromabout 0.05 to about 95 percent by weight of the active compounds of thisinvention. In a preferred embodiment of this invention, the herbicidalcompositions will comprise from about 5 to about 75 percent by weight ofthe active compound. The compositions can also comprise such additionalsubstances as other pesticides, such as insecticides, nematocides,fungicides, and the like; stabilizers, spreaders, deactivators,adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, dessicants growth inhibitors,and the like in the herbicidal compositions heretofore described. Theseother materials can comprise from about 5% to about 95% of the activeingredients in the herbicidal compositions. Use of combinations of theseother herbicides and/or defoliants, dessicants, etc. With the compoundsof the present invention provide herbicidal compositions which are moreeffective in controlling weeds and often provide results unattainablewith separate compositions of the individual herbicides. The otherherbicides, defoliants, dessicants and plant growth inhibitors, withwhich the compounds of this invention can be used in the herbicidalcompositions to control weeds, can include chlorophenoxy herbicides suchas 2,4-D, 2,4,5-T, MCPA, MCPB, 4-(2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP,2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like; carbamate herbicidessuch as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like;thiocarbamate and dithiocarbamate herbicides such as CDEC, methamsodium, EPTC, diallate, PEBC, perbulate, vernolate and the like;substituted urea herbicides such as norea, siduron, dichloral urea,chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron,monolinuron, neburon, buturon, trimeturon and the like, symmetricaltriazine herbicides such as simazine, chloroazine, atraone, desmetryne,norazine, ipazine, prometryn, atrazine, trietazine, simetone, prometone,propazine, ametryne and the like; chloroacetamide herbicides such asalpha-chloro-N,N-dimethylacetamide, CDEA, CDAA,alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide,4-(chloroacetyl)morpholine, 1-(chloroacetyl)piperidine and the like;chlorinated aliphatic acid herbicides such as TCA, dalapon,2,3-dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoicacid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA,dicamba, tricamba, amiben, fenac, PBA,2-methoxy-3,6-dichlorophenylacetic acid,3-methoxy-2,6-dichlorophenylacetic acid,2-methoxy-3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoicacid and the like; and such compounds as aminotriazole, maleichydrazide, phenyl mercuric acetate, endothal, biuret, technicalchlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquate, erbon,DNC, DNBP, dichlobenil, DPA, diphenamid, dipropalin, trifluralin, solan,dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin,bensulfide, AMS, bromacil,2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione,bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone,diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassiumcyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP,picloram, DPA, PCA, pyrichlor, sesone, terbacil, terbutol, TCBA,brominil, CP-50144, H-176-1, H-732, M-2901, planavin, sodiumtetraborate, calcium cyanamide, DEF, ethyl xanthogen disulfide, sindone,sindone B, propanil and the like. Such herbicides can also be used inthe methods and compositions of this invention in the form of theirsalts, esters, amides, and other derivatives whenever applicable to theparticular parent compounds.

Weeds are undesirable plants growing where they are not wanted, havingno economic value, and interfering with the production of cultivatedcrops, with the growing of ornamental plants, or with the welfare oflivestock. Many types of weeds are known, including annuals such aspigweed, lambsquarters, foxtail, crabgrass, wild mustard, fieldpennycress, ryegrass, goose grass, chickweed, wild oats, velvetleaf,purslane, barnyardgrass, smartweed, knotweed, cocklebur, wild buckwheat,kochia, medic, corn cockle, ragweed, sow-thistile, coffeeweed, croton,cuphea, dodder, fumitory, groundsel, hemp nettle, knawel, spurge,spurry, emex, jungle rice, pondweed, dog fennel, carpetweed,morningglory, bed-straw, ducksalad, naiad, cheatgrass, fall panicum,jimsonweed, witchgrass, switchgrass, watergrass, teaweed, wild turnipand sprangletop; biennials such as wild carrot, matricaria, wild barley,campion, chamomile, burdock, mullein, roundleaved mallow, bull thistile,bounds-tongue, moth mullein and purple star thistle; or perennials suchas white cockle, perennial ryegrass, quackgrass, Johnsongrass, Canadathistle, hedge bindweed, Bermuda grass, sheep sorrel, curly dock,nutgrass, field chickweed, dandelion, campanula, field bindweed, Russianknapweed, mesquite, toadflax, yarrow, aster, gromwell, hosetail,ironweed, sesbania, bulrush, cattail, winter-cress, horsenettle,nutsedge, milkweed and sicklepod.

Similarly, such weeds can be classified as broadleaf or grassy weeds. Itis economically desirable to control the growth of such weeds withoutdamaging beneficial plants or livestock.

The new compounds of this invention are particularly valuable for weedcontrol because they are toxic to many species and groups of weeds whilethey are relatively nontoxic to many beneficial plants. The exact amountof compound required will depend on a variety of factors, including thehardiness of the particular weed species, weather, type of soil, methodof application, the kind of beneficial plants in the same area and thelike. Thus, while the application of up to only about one or two ouncesof active compound per acre may be sufficient for good control of alight infestation of weeds growing under adverse conditions, theapplication of ten pounds or more of an active compound per acre may berequired for good control of a dense infestation of hardy perennialweeds growing under favorable conditions.

The herbicidal toxicity of the new compounds of this invention can bedemonstrated by the following established testing techniques known tothe art, pre- and post-emergence testing.

The herbicidal activity of the compounds of this invention can bedemonstrated by experiments carried out for the pre-emergence control ofa variety of weeds. In these experiments small plastic greenhouse potsfilled with dry soil are seeded with the various weed seeds. Twenty-fourhours or less after seeding the pots are sprayed with water until thesoil is wet and a test compound formulated as an aqueous emulsion of anacetone solution containing emulsifiers is sprayed at the desiredconcentrations on the surface of the soil.

After spraying, the soil containers are placed in the greenhouse andprovided with supplementary heat as required and daily or more frequentwatering. The plants are maintained under these conditions for a periodof from 15 to 21 days, at which time the condition of the plants and thedegree of injury to the plants is rated on a scale of from 0 to 10, asfollows: 0 = no injury, 1,2 = slight injury, 3,4 = moderate injury, 5,6= moderately severe injury, 7,8,9 = severe injury and 10 = death.

The herbicidal activity of the compounds of this invention can also bedemonstrated by experiments carried out for the post-emergence controlof a variety of weeds. In these experiments the compounds to be testedare formulated as aqueous emulsions and sprayed at the desired dosage onthe foliage of the weeds that have attained a prescribed size. Afterspraying the plants are placed in a greenhouse and watered daily or morefrequently. Water is not applied to the foliage of the treated plants.The severity of the injury is determined 10 to 15 days after treatmentand is rated on the scale of from 0 to 10 heretofore described.

We claim:
 1. A compound of the formula ##STR15## wherein X is selectedfrom the group consisting of lower alkyl, chlorine, bromine, fluorine,lower chloroalkyl, lower bromoalkyl, trifluoromethyl, and lower alkoxy;n is an integer from 0 to 2; R¹ is selected from the group consisting oflower alkyl, lower alkenyl, lower haloalkyl and ##STR16## wherein R⁴ andR⁵ are each selected from the group consisting of hydrogen and alkyl ofup to 3 carbon atoms; and R² and R³ are each selectd from the groupconsisting of hydrogen, lower alkyl, lower alkenyl, lower haloalkyl,lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbonatoms and ##STR17## where p is the integer 0 or 1; Y is selected fromthe group consisting of lower alkyl, lower alkoxy, lower alkylthio,halogen lower chloroalkyl, lower bromoalkyl, trifluoromethyl, nitro andcyano; and m is an integer from 0 to
 3. 2. The compound of claim 1,1-benzothiazl-2-yl-3-methyl-5-ethylamino-1,3-imidazolidin-2-one.
 3. Thecompound of claim 1,1-(5-methylbenzothiazol-2-yl)-3-methyl-5-t-butylamino-1,3-imidazolidin-2-one.4. The compound of claim 1,1-(6-chlorobenzothiazol-2-yl)-3-allyl-5-allylamino-1,3-imidazolidin-2-one.5. The compound of claim 1,1-(7-bromobenzothiazol-2-yl)-3-propargyl-5-β-chloroethylamino-1,3-imidazolidin-2-one.6. The compound of claim 1,1-(4-methoxybenzothiazol-2-yl)-3-ethyl-5-β-hydroxyethylamino-1,3-imidazolidin-2-one.7. The compound of claim 1,1-(5-fluorobenzothiazol-2-yl)-3-chloromethyl-5-methoxymethylamino-1,3-imidazolidin2-one.8. The compound of claim 1,1-(5-trifluoromethyl-benzothiazol-2-yl)-3-β-bromoethyl-5-cyclopropylamino-1,3-imidazolidin-2-one.9. The compound of claim 1,1-benzothiazol-2-yl-3-methyl-5-anilino-1,3-imidazolidin-2-one.